CN105926021A - Preparation method and application of nickel phosphide nano film - Google Patents
Preparation method and application of nickel phosphide nano film Download PDFInfo
- Publication number
- CN105926021A CN105926021A CN201610177542.5A CN201610177542A CN105926021A CN 105926021 A CN105926021 A CN 105926021A CN 201610177542 A CN201610177542 A CN 201610177542A CN 105926021 A CN105926021 A CN 105926021A
- Authority
- CN
- China
- Prior art keywords
- nickel
- film
- foam
- nano thin
- phosphide nano
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/34—Anodisation of metals or alloys not provided for in groups C25D11/04 - C25D11/32
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/08—Other phosphides
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses a preparation method of a nickel phosphide nano film. The method comprises the following steps: (1) cleaning and drying the foam nickel; (2) using the foam nickel after cleaning and drying in the step (1) as an anode, and conducting anodic oxidation by using a DC stable power supply in an oxalic acid solution to obtain nickel oxalate @ nickel foam; (3) placing the nickel oxalate @ nickel foam prepared in the step (2) in the middle of a tube furnace, placing sodium hypophosphite in the downstream of the tube furnace, and setting temperature control procedures in an inert gas stream as below: heating at the rate of 2-4 DEG C / min to 380-450 DEG C, maintaining for 2-4 h, and then cooling to room temperature naturally to obtain the nickel phosphide nano film. The method employs first anodic oxidation, and then low temperature phosphatization to prepare the nickel phosphide nano film. Compared with other methods, the method has no addition of nickel source in the preparation process, and is simple, rapid effective and economical.
Description
Technical field
The invention belongs to technical field of nano material, be specifically related to a kind of nickel phosphide nano thin-film and its preparation method and application.
Background technology
Nano material refers to the most one-dimensional be in nanoscale scope (1～100nm) or the material being made up of them as elementary cell, and this is about as much as the yardstick that 10～100 atoms are arranged closely together.Nano material can be divided into three-dimensional material, two-dimensional material and zero dimension material by dimension.Nano material is studied by every field because showing special performance at micro-scale widely in last decade.Wherein at materials chemistry, physics, bioscience, new forms of energy science and computational science also have relevant theoretical research.
The a large amount of consumption of fossil fuels in the world today, result in Fossil fuel and will be faced with the crisis of exhaustion, so tapping a new source of energy is instant problem of studying now.Wherein new forms of energy include solar energy, wind energy, water energy, heat energy, nuclear energy and bioenergy etc..And hydrogen is a kind of high heating value, the energy of cleaning.Because with the presence of substantial amounts of water on the earth, can be as preparing the raw material sources of hydrogen, so hydrogen has the great potential as main energy sources from now on.Hydrone to be prepared as hydrogen, and to be done is exactly to be disconnected by the hydrogen-oxygen key in hydrone under the conditions of low activation energy.Therefore find a kind of durable and efficient catalyst for electrolysis elutriation hydrogen in the urgent need to.In addition it is known that in terms of liberation of hydrogen catalysis, noble metal shows the performance of excellence and is studied widely, but the shortcoming being limited to the rarity of Precious Metals Resources and high cost, energy problem that we are faced is the most unpractical to want to utilize noble metal catalyst to solve.So current study hotspot focuses on prepares efficient and stable non-precious metal catalyst.And material typically exhibits peculiar performance under nanoscale, therefore a lot of scholar's research prepares the non-precious metal catalyst of nanoscale, in preparing efficient and stable liberation of hydrogen catalyst.Energy problem is solved further by preparing the catalyst of efficient stable.
Hydrogen Energy has wide material sources, the advantages such as rich reserves, character are superior, and is considered as the preferable clean energy resource of 21st century.Particularly as follows:
(1) safety and environmental protection
Hydrogen molecule amount is 2, is the 1/14 of air, and therefore, hydrogen gas leakage can flee from ground in air automatically, will not form gathering.And other fuel-firing gas-firings all can be assembled ground and constitute inflammable and explosive danger.Nonpoisonous and tasteless, do not result in human body poisoning, combustion product is only water, free from environmental pollution.
(2) rich reserves, calorific value is high
Protium is the element that nature the most generally exists, it is estimated that the 75% of mass of the universe is all to be made up of it, and hydrogen is mainly stored in water with the form of compound, and water is materials most on the earth.It is estimated that, if the hydrogen in water being extracted preparation completely become hydrogen, bigger than all of Fossil fuel liberated heat on the burning earth 9000 times of the total amount of heat that its burning produces is gone back big.In addition to nuclear fuel, the calorific capacity of hydrogen is the highest in all chemical fuels, bio-fuel and Fossil fuel, and for 142.351kJ/kg, calorific capacity is 3 times of gasoline.
(3) automatic regeneration
Hydrogen and oxygen are by chemical reaction, and product is free of contamination water, discharges substantial amounts of energy simultaneously, is used for being converted into electric energy, mechanical energy, heat energy etc..Wherein the water of product can be hydrogen by electrolysis or photolytic conversion again.Whole process is simple, pollution-free.
(4) can use widely
After continue in May, 1976, the U.S. develops the vehicle of a kind of hydrogen fuel, Japan the most successfully develops a kind of liquified hydrogen fuel automobile；Late 1970s, the hydrogen powered vehicle of Mercedes-Benz motor corporation of Germany test, it is only necessary to the hydrogen fuel of five kilograms, automobile can travel 110 kilometers.Liquified hydrogen can also be as aircraft, the fuel of automobile, it is also possible to as rocket and the fuel of guided missile.The Lunar Probe Project Apollo Personnel investigation Program of the U.S. " first artificial satellite of number airship and China launch used by Long March carrier rocket, be all to use liquified hydrogen as fuel.Nikkei BP clean technologies institute speculates, the market scale to the year two thousand fifty whole world hydrogen-based Infrastructure is up to about 16,000,000,000,000 yen (1.3 trillion dollars).Hydrogen energy source can be by burning release chemical energy, it is also possible to be electric energy by fuel cells convert, it is also possible to be applied to nuclear fusion.Investigating according to USDOE (DOE) new energy development center, in past 5 years, it is 20.5% that global industrialized country puts into annual progressive increase rate to the exploitation of hydrogen energy source.These all show, and hydrogen energy source is no matter industrial in army or civilian industry is widely used.
Summary of the invention
The technical problem to be solved in the present invention is to overcome existing defect, it is provided that a kind of nickel phosphide nano thin-film, and this nickel phosphide nano thin-film can use as a kind of Electrocatalytic Activity for Hydrogen Evolution Reaction agent.
First purpose of the present invention is to provide the preparation method of a kind of nickel phosphide nano thin-film, and step is as follows:
(1) it is dried after nickel foam being cleaned；
(2) using the nickel foam after cleaning-drying in step (1) as anode, with DC stable power supply, in oxalic acid solution, anodic oxidation is carried out；Obtain nickel oxalate@nickel foam；
(3) nickel oxalate@nickel foam prepared by step (2) is placed on the centre of tube furnace, sodium hypophosphite is placed on tube furnace downstream, under inert gas flow, arranging temperature control program is: heating rate 2～4 DEG C/min, after 380～450 DEG C, maintain 2～4h, then naturally cool to room temperature, obtain nickel phosphide nano thin-film.
As preferably, cleaning described in step (1) is by first for nickel foam supersound process, the most respectively supersound process in acetone and ultra-pure water in dilute hydrochloric acid；
As further preferably, being dried described in step (1) is in vacuum drying oven, 35-45 DEG C of drying.
The reason being dried in this temperature range is: temperature is too high, can have an impact the performance of material, and temperature is the lowest, dries the time needed the most long.
As preferably, in step (2), the concentration of described oxalic acid solution is 0.15～0.35mol/L.
In the range of this, oxalic acid solution chemical property is best, if solubility is excessive, load capacity also increases, and stability can reduce.
As preferably, in step (2), described anodised condition is: voltage is 25～30V, and temperature is-5～0 DEG C, and the time is 5～10min.
This step uses anodised advantage to be simple to operate, rapidly.
As preferably, in step (2), after described anodic oxidation, also include the step cleaned, be dried；
As further preferably, described cleaning is to be carried out with a large amount of water and dehydrated alcohol；
It is to remove the impurity such as surface organic matter and oxide with water and washes of absolute alcohol.
As further preferably, described being dried is in vacuum drying oven, 55-65 DEG C of drying.
Drying temperature the highest, can have an impact the performance of material, temperature is too low, and the used time can be long；Therefore, select to dry in this temperature range.
As preferably, in step (3), the sodium hypophosphite of the nickel oxalate@nickel foam of every piece of 2 × 4cm corresponding 0.1～0.5g；
Sodium hypophosphite consumption in the reason of this scope is: very little, material will not be by complete phosphatization, and sodium hypophosphite is too many, and the pattern of material can be destroyed for sodium hypophosphite.
As further preferably, the distance between described nickel oxalate@nickel foam and sodium hypophosphite is 4-6cm.
Distance is too near, and pattern is had an impact by the phosphine gas pressure relatively conference that sodium hypophosphite discharges, and away from too far away, pressure is the least, and phosphatization is incomplete.
Second object of the present invention is to provide the nickel phosphide nano thin-film applying any of the above-described method to prepare.
Third object of the present invention is to provide any of the above-described nickel phosphide nano thin-film as the application in Electrocatalytic Activity for Hydrogen Evolution Reaction agent.
Fourth object of the present invention is to provide a kind of Electrocatalytic Activity for Hydrogen Evolution Reaction agent, and described Electrocatalytic Activity for Hydrogen Evolution Reaction agent is any of the above-described described nickel phosphide nano thin-film.
5th purpose of the present invention is to provide a kind of method being electrolysed elutriation hydrogen, using any of the above-described described nickel phosphide nano thin-film as working electrode, is electrolysed with 0.5M sulfuric acid solution for electrolyte.
Beneficial effects of the present invention is as follows:
1, the present invention is first with anodic oxidation, then is prepared for nickel phosphide nano thin-film through the method for low temperature phosphor, and compared with other method, the present invention, in preparation process, does not add any nickel source, the preparation method of the present invention simply rapidly and also economical and effective；
Although 2, anode oxidation method is a kind of method of the simple economy preparing nano material, but on nickel and alloy thereof, how to complete oxidation, not yet having been reported that at present, the application has obtained a kind of anode oxidation method using nickel as substrate by research, creates the compound with nickel as substrate；
3, the present invention uses nickel phosphide nano thin-film as Electrocatalytic Activity for Hydrogen Evolution Reaction agent, and overpotential is 175mV, and Tafel slope is 78mV/dec, good endurance.
Accompanying drawing explanation
Accompanying drawing is for providing a further understanding of the present invention, and constitutes a part for description, is used for together with embodiments of the present invention explaining the present invention, is not intended that limitation of the present invention.In the accompanying drawings:
Fig. 1 is the Electronic Speculum figure of NiP/Ni Foam nano thin-film prepared by the present invention；
Fig. 2 is NiP/Ni Foam nano thin-film Tafel slope figure prepared by the present invention；
Fig. 3 is in 0.5M sulfuric acid solution, initial and after 1000 circle CV (-0.2～0.2vs RHE sweeps speed 100mV/s) the polarization curve (leftmost curve) of NiP/Ni foam nano thin-film prepared by the present invention；
Fig. 4 is the NiP/Ni foam nano thin-film overpotential at 175mV of the present invention, continues the time m-current density plot of 24h；
Fig. 5 is gained Ni Foam (leftmost curve) of the present invention, the cathodic polarization curve of NiO/Ni Foam (intermediate curve), NiP/Ni Foam (right side graph) the electrolysis elutriation hydrogen in 0.5M sulfuric acid solution.
Detailed description of the invention
Below example facilitates a better understanding of the present invention, but does not limit the present invention.Experimental technique in following embodiment, if no special instructions, is conventional method.Test material used in following embodiment, if no special instructions, is commercially available.
The water used in embodiment is redistilled water, and the reagent used by experiment is analytical pure.Experiment is carried out the most at the corresponding temperature.
Instrument used in embodiment and reagent
CHI832 electrochemical analyser (Shanghai Chen Hua instrument company) is used for linear sweep voltammetry curve experiments；Saturated silver/silver chloride electrode (Shanghai Dao scientific instrument company limited)；The automatic dual pure water distillator of quartz ampoule heated type (1810B, Asian-Pacific Glass-Tech. Co., Shanghai City) is used for preparing redistilled water；Electronic balance (Beijing Sai Duolisi Instrument Ltd.) is used for weighing medicine；JSM-6701F cold field emission type scanning electron microscope (Jeol Ltd.) is used for nickel phosphide nano thin-film morphology characterization；Ultrasonic cleaner (Kunshan Ultrasonic Instruments Co., Ltd.).
The preparation method of the nickel phosphide nano thin-film of the present invention is:
1) nickel foam of business is cut into the specification of 2 × 4cm, first in the dilute hydrochloric acid of 2～4mol/l ultrasonic 15～25min, remove oxide and some foreign material on surface, the most respectively in acetone and ultra-pure water each ultrasonic 15～25min, this process is the most at room temperature carried out, then rinses with a large amount of water, to remove the impurity such as oxide on surface and Organic substance, being finally putting in vacuum drying oven, 35-45 DEG C of drying is stand-by；
2) anodic oxidation: using step 1) nickel foam of institute's wash clean is as anode, with DC stable power supply, in the oxalic acid solution of 0.15～0.35mol/L, carrying out anodic oxidation, setting voltage is 25～30V, temperature is-5～0 DEG C, time is 5～10min, gained sample a large amount of water and washes of absolute alcohol after reaction, then, 55-65 DEG C of drying in vacuum drying oven, obtains nickel oxalate@nickel foam；
3) by step 2) prepared by a piece of nickel oxalate@nickel foam be placed on the centre of tube furnace, 0.1～0.5g sodium hypophosphite is placed on tube furnace downstream, and the distance between them is 4-6cm.Under inert gas flow, such as argon flows down, and arranges temperature control program and is: heating rate 2～4 DEG C/min, and 380～450 DEG C maintain 2～4h, then naturally cools to room temperature, and obtained material takes out, obtains nickel phosphide nano thin-film.
Embodiment 1
The preparation method of the nickel phosphide nano thin-film of the present invention is:
1) nickel foam of business is cut into the specification of 2 × 4cm, first ultrasonic 15min in the dilute hydrochloric acid of 3mol/l, remove oxide and some foreign material on surface, each ultrasonic 15min in acetone and ultra-pure water the most respectively, this process is the most at room temperature carried out, then rinses with a large amount of water, to remove the impurity such as oxide on surface and Organic substance, being finally putting in vacuum drying oven, 40 DEG C of drying are stand-by；
2) anodic oxidation: using step 1) nickel foam of institute's wash clean is as anode, with DC stable power supply, in the oxalic acid solution of 0.25mol/L, carrying out anodic oxidation, setting voltage is 25V, temperature is-5 DEG C, time is 10min, gained sample a large amount of water and washes of absolute alcohol after reaction, then, 60 DEG C of drying in vacuum drying oven, obtain nickel oxalate@nickel foam；
3) by step 2) prepared by a piece of nickel oxalate@nickel foam be placed on the centre of tube furnace, 0.1g sodium hypophosphite is placed on tube furnace downstream, and the distance between them is 4-6cm.Flowing down at argon, arranging temperature control program is: 2 DEG C/min of heating rate, and 380 DEG C maintain 2h, then naturally cools to room temperature, and obtained material takes out, obtains nickel phosphide nano thin-film.Observing with JSM-6701F cold field emission type scanning electron microscope, observed result sees Fig. 1.
By the Electronic Speculum figure of Fig. 1, be apparent from finds out the nickel foam having obtained having loaded one layer of nickel phosphide thin film.The thickness of nano thin-film is 200～300nm.
The chemical formula being obtained NiP/Ni Foam by nickel oxalate@nickel foam is as follows:
NiO+H2O→Ni(OH)2
NI2++H2PO2 -+2H+→NiP+2H2O
The nickel phosphide nano thin-film obtained is carried out performance test.Test result sees Fig. 2-Fig. 4.
Fig. 2 is NiP/Ni Foam nano thin-film Tafel slope figure prepared by the present invention.
As seen from Figure 2, when the overpotential of NiP/Ni Foam nano thin-film prepared by the application is in the range of 50-200mV, η Yu log (mA/cm2) linear, meet Tafel equation, be 78mV/decade through matching Tafel slope.
Fig. 3 is in 0.5M sulfuric acid solution, initial and after 1000 circle CV (-0.2～0.2vs RHE sweeps speed 100mV/s) the polarization curve (leftmost curve) of NiP/Ni foam nano thin-film prepared by the present invention；
As seen from Figure 3, in 0.5M sulfuric acid solution, initial and after 1000 circle CV (-0.2～0.2vs RHE sweeps speed 100mV/s) polarization curve (leftmost curve) contrasts understand；The polarization curve electric current of NiP/Ni foam composite prepared by the present invention is almost without any loss.
Fig. 4 is the NiP/Ni foam nano thin-film overpotential at 175mV of the present invention, continues the time m-current density plot of 24h.
As seen from Figure 4, this catalyst is when stable overpotential is 175mV, and experience is when the continuous firing of 24h, and electric current density is almost without the trend reduced, and this test shows that composite has the stability of excellence.
Embodiment 2
The preparation method of the nickel phosphide nano thin-film of the present invention is:
1) nickel foam of business is cut into the specification of 2 × 4cm, first ultrasonic 25min in the dilute hydrochloric acid of 2mol/l, remove oxide and some foreign material on surface, each ultrasonic 20min in acetone and ultra-pure water the most respectively, this process is the most at room temperature carried out, then rinses with a large amount of water, to remove the impurity such as oxide on surface and Organic substance, being finally putting in vacuum drying oven, 40 DEG C of drying are stand-by；
2) anodic oxidation: using step 1) nickel foam of institute's wash clean is as anode, with DC stable power supply, in the oxalic acid solution of 0.15mol/L, carrying out anodic oxidation, setting voltage is 30V, temperature is-2 DEG C, time is 8min, gained sample a large amount of water and washes of absolute alcohol after reaction, then, 65 DEG C of drying in vacuum drying oven, obtain nickel oxalate@nickel foam；
3) by step 2) prepared by a piece of nickel oxalate@nickel foam be placed on the centre of tube furnace, 0.5g sodium hypophosphite is placed on tube furnace downstream, and the distance between them is 4cm.Flowing down at argon, arranging temperature control program is: 4 DEG C/min of heating rate, and 400 DEG C maintain 4h, then naturally cools to room temperature, and obtained material takes out, obtains nickel phosphide nano thin-film.
Embodiment 3
The preparation method of the nickel phosphide nano thin-film of the present invention is:
1) nickel foam of business is cut into the specification of 2 × 4cm, first ultrasonic 20min in the dilute hydrochloric acid of 4mol/l, remove oxide and some foreign material on surface, each ultrasonic 25min in acetone and ultra-pure water the most respectively, this process is the most at room temperature carried out, then rinses with a large amount of water, to remove the impurity such as oxide on surface and Organic substance, being finally putting in vacuum drying oven, 35 DEG C of drying are stand-by；
2) anodic oxidation: using step 1) nickel foam of institute's wash clean is as anode, with DC stable power supply, in the oxalic acid solution of 0.35mol/L, carrying out anodic oxidation, setting voltage is 28V, temperature is 0 DEG C, time is 5min, gained sample a large amount of water and washes of absolute alcohol after reaction, then, 55 DEG C of drying in vacuum drying oven, obtain nickel oxalate@nickel foam；
3) by step 2) prepared by a piece of nickel oxalate@nickel foam be placed on the centre of tube furnace, 0.3g sodium hypophosphite is placed on tube furnace downstream, and the distance between them is 6cm.Flowing down at argon, arranging temperature control program is: 2 DEG C/min of heating rate, and 450 DEG C maintain 2h, then naturally cools to room temperature, and obtained material takes out, obtains nickel phosphide nano thin-film.
Embodiment 4
The preparation method of the nickel phosphide nano thin-film of the present invention is:
1) nickel foam of business is cut into the specification of 2 × 4cm, first ultrasonic 25min in the dilute hydrochloric acid of 3mol/l, remove oxide and some foreign material on surface, each ultrasonic 15min in acetone and ultra-pure water the most respectively, this process is the most at room temperature carried out, then rinses with a large amount of water, to remove the impurity such as oxide on surface and Organic substance, being finally putting in vacuum drying oven, 45 DEG C of drying are stand-by；
2) anodic oxidation: using step 1) nickel foam of institute's wash clean is as anode, with DC stable power supply, in the oxalic acid solution of 0.20mol/L, carrying out anodic oxidation, setting voltage is 26V, temperature is-3 DEG C, time is 7min, gained sample a large amount of water and washes of absolute alcohol after reaction, then, 58 DEG C of drying in vacuum drying oven, obtain nickel oxalate@nickel foam；
3) by step 2) prepared by a piece of nickel oxalate@nickel foam be placed on the centre of tube furnace, 0.4g sodium hypophosphite is placed on tube furnace downstream, and the distance between them is 5cm.Flowing down at argon, arranging temperature control program is: 3 DEG C/min of heating rate, and 410 DEG C maintain 3h, then naturally cools to room temperature, and obtained material takes out, obtains nickel phosphide nano thin-film.
Embodiment 5
The preparation method of the nickel phosphide nano thin-film of the present invention is:
1) nickel foam of business is cut into the specification of 2 × 4cm, first ultrasonic 20min in the dilute hydrochloric acid of 3mol/l, remove oxide and some foreign material on surface, each ultrasonic 22min in acetone and ultra-pure water the most respectively, this process is the most at room temperature carried out, then rinses with a large amount of water, to remove the impurity such as oxide on surface and Organic substance, being finally putting in vacuum drying oven, 38 DEG C of drying are stand-by；
2) anodic oxidation: using step 1) nickel foam of institute's wash clean is as anode, with DC stable power supply, in the oxalic acid solution of 0.30mol/L, carrying out anodic oxidation, setting voltage is 28V, temperature is-4 DEG C, time is 8min, gained sample a large amount of water and washes of absolute alcohol after reaction, then, 63 DEG C of drying in vacuum drying oven, obtain nickel oxalate@nickel foam；
3) by step 2) prepared by a piece of nickel oxalate@nickel foam be placed on the centre of tube furnace, 0.2g sodium hypophosphite is placed on tube furnace downstream, and the distance between them is 4cm.Flowing down at argon, arranging temperature control program is: 4 DEG C/min of heating rate, and 420 DEG C maintain 2.5h, then naturally cools to room temperature, and obtained material takes out, obtains nickel phosphide nano thin-film.
Embodiment 6
The method that the nickel phosphide nano thin-film of the application present invention prepares electrode is as follows:
The prepared nickel foam shears being loaded with NiP nano thin-film is cut to the specification of 0.5cm × 1.0cm, standby as working electrode.
Embodiment 7
As follows as the specific experiment of liberation of hydrogen catalyst using the electrode that the embodiment of the present invention prepares:
The prepared nickel foam shears being loaded with NiP nano thin-film is cut to the specification of 0.5cm × 1.0cm, standby as working electrode.Using platinum electrode as to electrode, saturated silver/silver chloride electrode is as reference electrode.The electrolyte of LSV and CV uses the H of 0.5M2SO4。
In electrochemical workstation, selecting linear sweep voltammetry curve and i-t curve, silver/silver chloride is reference electrode, and platinum filament is to electrode, and the electrode that the present invention prepares is working electrode；
As shown in Figure 5, gained Ni Foam (leftmost curve) of the present invention, the cathodic polarization curve of NiO/Ni Foam (intermediate curve), NiP/Ni Foam (right side graph) the electrolysis elutriation hydrogen in 0.5M sulfuric acid solution.It can be seen that electrolysis elutriation hydrogen activity (leftmost curve) of nickel foam is the most weak, form a sharp contrast with this: cover nickel phosphide thin film nickel foam and obtain electrolysis elutriation hydrogen activity best in these several catalyst.
Last it is noted that the foregoing is only the preferred embodiments of the present invention, it is not limited to the present invention, although the present invention being described in detail with reference to previous embodiment, for a person skilled in the art, technical scheme described in foregoing embodiments still can be modified by it, or wherein portion of techniques feature is carried out equivalent.All within the spirit and principles in the present invention, any modification, equivalent substitution and improvement etc. made, should be included within the scope of the present invention.
Claims (10)
1. the preparation method of a nickel phosphide nano thin-film, it is characterised in that: step is as follows:
(1) it is dried after nickel foam being cleaned；
(2) using the nickel foam after cleaning-drying in step (1) as anode, with DC stable power supply, in oxalic acid solution, anodic oxidation is carried out；Obtain nickel oxalate@nickel foam；
(3) nickel oxalate@nickel foam prepared by step (2) is placed on the centre of tube furnace, sodium hypophosphite is placed on tube furnace downstream, under inert gas flow, arranging temperature control program is: heating rate 2～4 DEG C/min, after 380～450 DEG C, maintain 2～4h, then naturally cool to room temperature, obtain nickel phosphide nano thin-film.
Method the most according to claim 1, it is characterised in that: cleaning described in step (1) is by first for nickel foam supersound process, the most respectively supersound process in acetone and ultra-pure water in dilute hydrochloric acid；
As preferably, being dried described in step (1) is in vacuum drying oven, 35-45 DEG C of drying.
Method the most according to claim 1, it is characterised in that: in step (2), the concentration of described oxalic acid solution is 0.15～0.35mol/L.
Method the most according to claim 1, it is characterised in that: in step (2), described anodised condition is: voltage is 25～30V, and temperature is-5～0 DEG C, and the time is 5～10min.
Method the most according to claim 1, it is characterised in that: in step (2), after described anodic oxidation, also include the step cleaned, be dried；
As preferably, described cleaning is to be carried out with a large amount of water and dehydrated alcohol；
As preferably, described being dried is in vacuum drying oven, 55-65 DEG C of drying.
Method the most according to claim 1, it is characterised in that: in step (3), the sodium hypophosphite of the nickel oxalate@nickel foam of every piece of 2 × 4cm corresponding 0.1～0.5g；
As preferably, the distance between described nickel oxalate@nickel foam and sodium hypophosphite is 4-6cm.
7. the nickel phosphide nano thin-film that the arbitrary described method of application claim 1-6 prepares.
8. the nickel phosphide nano thin-film described in claim 7 is as the application in Electrocatalytic Activity for Hydrogen Evolution Reaction agent.
9. an Electrocatalytic Activity for Hydrogen Evolution Reaction agent, it is characterised in that: described Electrocatalytic Activity for Hydrogen Evolution Reaction agent is the arbitrary described nickel phosphide nano thin-film of claim 1-6.
10. the method being electrolysed elutriation hydrogen, it is characterised in that: using arbitrary for claim 1-6 described nickel phosphide nano thin-film as working electrode, it is electrolysed with 0.5M sulfuric acid solution for electrolyte.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610177542.5A CN105926021B (en) | 2016-03-24 | 2016-03-24 | A kind of nickel phosphide nano thin-film and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610177542.5A CN105926021B (en) | 2016-03-24 | 2016-03-24 | A kind of nickel phosphide nano thin-film and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105926021A true CN105926021A (en) | 2016-09-07 |
| CN105926021B CN105926021B (en) | 2018-02-27 |
Family
ID=56840355
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610177542.5A Expired - Fee Related CN105926021B (en) | 2016-03-24 | 2016-03-24 | A kind of nickel phosphide nano thin-film and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105926021B (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106486680A (en) * | 2016-11-07 | 2017-03-08 | 济南大学 | A kind of preparation method of phosphatization stainless steel electrolytic water catalysis material |
| CN106498434A (en) * | 2016-11-04 | 2017-03-15 | 重庆工商大学 | The preparation method of the Ni-based porous nickel phosphide hydrogen-precipitating electrode of integration |
| CN106807416A (en) * | 2017-01-12 | 2017-06-09 | 南开大学 | A kind of self-supporting nickel phosphide nanometer sheet material of electrocatalytic decomposition water hydrogen manufacturing and preparation method thereof |
| CN107651656A (en) * | 2017-09-15 | 2018-02-02 | 电子科技大学 | A kind of Ni2P4O12Nano-particle material and its preparation method and application |
| CN107694584A (en) * | 2017-10-15 | 2018-02-16 | 华东师范大学 | A kind of self-supporting catalyst of phosphatizing nickel and its preparation method and application |
| CN108380228A (en) * | 2018-02-12 | 2018-08-10 | 华东理工大学 | A kind of preparation method and applications of nickel sulfide/nickel phosphide of 1 dimension/1 dimension nanometer construction assembling |
| CN110453253A (en) * | 2019-09-23 | 2019-11-15 | 合肥工业大学 | A kind of preparation method of sintered NdFeB magnet surface NiP alloy layer |
| CN111020624A (en) * | 2019-11-29 | 2020-04-17 | 哈尔滨工业大学 | Preparation method of high-frequency vibration corrosion self-supporting electrocatalyst |
| CN114408886A (en) * | 2022-01-26 | 2022-04-29 | 青岛科技大学 | Preparation of porous iron nickel phosphide doped with noble metal |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100430135C (en) * | 2006-10-19 | 2008-11-05 | 安徽师范大学 | Catalyst of phosphatizing nickel, and preparation method |
| CN101670292A (en) * | 2009-09-24 | 2010-03-17 | 南开大学 | Method for preparing Ni12P5 by reducing nickel oxide at low temperature |
| CN101327439B (en) * | 2008-08-01 | 2012-01-04 | 南开大学 | Hypophosphite precursor heat decomposition method for preparing Ni2P catalyst |
| CN101671009B (en) * | 2009-09-24 | 2012-04-25 | 南开大学 | Method for preparing Ni2P by reducing nickel oxide precursor through thermal treatment at low temperature |
| CN103466574A (en) * | 2013-09-17 | 2013-12-25 | 天津工业大学 | Method for preparing three-dimensional macroporous metal phosphide |
| CN104766725A (en) * | 2015-03-12 | 2015-07-08 | 广东工业大学 | Preparation method for electrode material used for supercapacitor and application of electrode material |
| CN104810165A (en) * | 2015-04-29 | 2015-07-29 | 华东理工大学 | Nickel phosphide / graphene composite film preparing method |
-
2016
- 2016-03-24 CN CN201610177542.5A patent/CN105926021B/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100430135C (en) * | 2006-10-19 | 2008-11-05 | 安徽师范大学 | Catalyst of phosphatizing nickel, and preparation method |
| CN101327439B (en) * | 2008-08-01 | 2012-01-04 | 南开大学 | Hypophosphite precursor heat decomposition method for preparing Ni2P catalyst |
| CN101670292A (en) * | 2009-09-24 | 2010-03-17 | 南开大学 | Method for preparing Ni12P5 by reducing nickel oxide at low temperature |
| CN101671009B (en) * | 2009-09-24 | 2012-04-25 | 南开大学 | Method for preparing Ni2P by reducing nickel oxide precursor through thermal treatment at low temperature |
| CN103466574A (en) * | 2013-09-17 | 2013-12-25 | 天津工业大学 | Method for preparing three-dimensional macroporous metal phosphide |
| CN104766725A (en) * | 2015-03-12 | 2015-07-08 | 广东工业大学 | Preparation method for electrode material used for supercapacitor and application of electrode material |
| CN104810165A (en) * | 2015-04-29 | 2015-07-29 | 华东理工大学 | Nickel phosphide / graphene composite film preparing method |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106498434A (en) * | 2016-11-04 | 2017-03-15 | 重庆工商大学 | The preparation method of the Ni-based porous nickel phosphide hydrogen-precipitating electrode of integration |
| CN106498434B (en) * | 2016-11-04 | 2018-08-17 | 重庆工商大学 | The preparation method of the Ni-based porous nickel phosphide hydrogen-precipitating electrode of integration |
| CN106486680A (en) * | 2016-11-07 | 2017-03-08 | 济南大学 | A kind of preparation method of phosphatization stainless steel electrolytic water catalysis material |
| CN106807416A (en) * | 2017-01-12 | 2017-06-09 | 南开大学 | A kind of self-supporting nickel phosphide nanometer sheet material of electrocatalytic decomposition water hydrogen manufacturing and preparation method thereof |
| CN107651656A (en) * | 2017-09-15 | 2018-02-02 | 电子科技大学 | A kind of Ni2P4O12Nano-particle material and its preparation method and application |
| CN107694584A (en) * | 2017-10-15 | 2018-02-16 | 华东师范大学 | A kind of self-supporting catalyst of phosphatizing nickel and its preparation method and application |
| CN107694584B (en) * | 2017-10-15 | 2021-06-22 | 华东师范大学 | Self-supporting nickel phosphide catalyst and preparation method and application thereof |
| CN108380228A (en) * | 2018-02-12 | 2018-08-10 | 华东理工大学 | A kind of preparation method and applications of nickel sulfide/nickel phosphide of 1 dimension/1 dimension nanometer construction assembling |
| CN110453253A (en) * | 2019-09-23 | 2019-11-15 | 合肥工业大学 | A kind of preparation method of sintered NdFeB magnet surface NiP alloy layer |
| CN111020624A (en) * | 2019-11-29 | 2020-04-17 | 哈尔滨工业大学 | Preparation method of high-frequency vibration corrosion self-supporting electrocatalyst |
| CN114408886A (en) * | 2022-01-26 | 2022-04-29 | 青岛科技大学 | Preparation of porous iron nickel phosphide doped with noble metal |
| CN114408886B (en) * | 2022-01-26 | 2023-12-22 | 青岛科技大学 | Preparation of noble metal doped porous iron-nickel phosphide |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105926021B (en) | 2018-02-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105926021A (en) | Preparation method and application of nickel phosphide nano film | |
| Lan et al. | Direct ammonia alkaline anion-exchange membrane fuel cells | |
| Li et al. | Performance and methane production characteristics of H2O–CO2 co-electrolysis in solid oxide electrolysis cells | |
| Gür | Mechanistic modes for solid carbon conversion in high temperature fuel cells | |
| Uchida et al. | High-performance electrode for steam electrolysis: mixed conducting ceria-based cathode with highly-dispersed Ni electrocatalysts | |
| Ni et al. | Ammonia‐fed solid oxide fuel cells for power generation—a review | |
| Ihara et al. | Quickly rechargeable direct carbon solid oxide fuel cell with propane for recharging | |
| Sasikumar et al. | Aqueous methanol eletrolysis using proton conducting membrane for hydrogen production | |
| Fornaciari et al. | The role of water in vapor-fed proton-exchange-membrane electrolysis | |
| Calabriso et al. | Performance investigation of passive direct methanol fuel cell in different structural configurations | |
| Ayers et al. | Efficient generation of high energy density fuel from water | |
| Wang et al. | Freezing site of super-cooled water and failure mechanism of cold start of PEFC | |
| Pandiyan et al. | CO2 conversion via coupled plasma-electrolysis process | |
| EP2450994B1 (en) | Process and apparatus of CO2 energy source adopted in solid oxide fuel cell - CO2 energy conversion cycle | |
| Alioshin et al. | High temperature electrolysis of CO2 for fuel production | |
| Dowd et al. | Performance evaluation of a hydrogen-vanadium reversible fuel cell | |
| Khalid et al. | Model development and analysis of a novel high-temperature electrolyser for gas phase electrolysis of hydrogen chloride for hydrogen production | |
| Maruyama et al. | Bifunctional oxygen electrodes with highly step-enriched surface of Fe–Nx containing carbonaceous thin film | |
| Peters et al. | Experimental results of a 10/40 kW-class reversible solid oxide cell demonstration system at forschungszentrum jülich | |
| Li et al. | Analysis of the Performance of Phosphorus and Sulphur Co-Doped Reduced Graphene Oxide as Catalyst in Vanadium Redox Flow Battery | |
| Zhou et al. | Simultaneous electrochemical reduction of carbon dioxide and partial oxidation of methane in a solid oxide cell with silver-based cathode and nickel-based anode | |
| Ippolito et al. | Effect of CeO2 addition on hybrid direct carbon fuel cell performance | |
| Edge et al. | Comparison of novel anode materials for the production of hydrogen using CuCl/HCl electrolyzers | |
| Yeager | Fuel Cells: They produce more electricity per pound of fuel than any other nonnuclear method of power production. | |
| Tomita et al. | Surface Modification of a Doped BaCeO3 to Function as an Electrolyte and as an Anode for SOFCs |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180227 Termination date: 20190324 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |